Indigoid dyestuffs



r formula Patented Nov. 17, 1925.

UNITED STATES PATENT OFFICE.

BERTRAM MAYER, OF BASEL, AND

SWITZERLAND, ASSIGNORS TO THE SOCIETY O F GEEMICAL INDUSTRY IN BASLE OF BASED, SWITZERLAND.

mnroorn nynszrurrs.

No. Drawing To all whom it may concern:

JAKOB WiiRsLnR, both citizens of the Swiss the former at Basel, Switzerland, and the latter at Neuewelt, near Basel, Switzerland, have invented new and useful Indigoid Dyestuffs, of which the following is a full, clear, and exact specification.

This invention relates to new indigoid dyestufis. It comprises the new dyestufi's, the process of making same, as well as the materials dyed with. the new dyestuffs.

In our Patents 1,527,894 Feb 2 1925 and'1,534,535 Apr. 21, 1925, new thioglycolo-carboxylic acids have been described cor-' responding most probably to the general s-cm-ooon 3 i I wherein a: may stand for a hydrogen atom or an oxygen atom). These thio lycol-ocarboxylic acids may be condense to the corresponding 0 hionaphthene derivatives having proba ly the general formula:

(wherein m may stand for a hydr en atom or an oxygen atom, audit for a ydrogen atom, an acidyl group or a carboxyl group) for instance y treating them wlth acetic anhydride and sodium acetate or by heatingthem in presence of a suitable solvent.

It has now been found that valuable new indi oid' dyestufl's'are obtained by reacting on tfie oxythionaphthene derivatives and the corresponding thioglycol-o-carboxylic acids above referred t wherein as O, halogen, atoms of which Applicationflled January 4, 1924. Serial No. 684,449.

group such m, n and 1' atoms adjacent to each other which at the same time appertain to an of which the third is N H -S aromatic ring system, and

-or G.

Such compounds are for instance fivemembered condensed ring systems, such as isatins, indoxyls,

oxythionaphthenes of lene, -anthracene acena ht'he'nequinones,

thioisatins; thioindoxyls or the benzene, naphthaand anthraquinone series,

and thelike, their homo ogues and substitution products, anils halides.

com onents in a con e'nsmg Also in that c agent, tion of OXldlZlIlg solvent which may act as a in certain cases by addiagents.

boxylic acid has been employed as astarting been formed.

dyestufi? does only with compounds having Be it known that we, BERTRAM MAYnRand the general formula:

place by heating the:

so where thioglycol-o-car- The dyestulfs thus obtained correspond to v the general formula: I

whereinz, r, m and n have the significations as has hereinbefore been defined. form red to green and black powders,

They which dissolve in concentrated sulphuric acid to orange-red to yieldlng with soda solution or which dye cotton grey tints.

can and brown solutions,

in the form of orange These dyestufls into the corresponding halogenated dyestuffs by subsequent halogenation.

\ The following examples illustrate the invention but without limitingit; the parts being by weight.

. Ewample 1..

1 part of anthraquinone fZ-thioglycol-3- carboxylic acid is cautiously heated with 0.2 part of anhydrous sodium acetate in 5 parts of acetic anh dride until evolution of carbon dioxide as ceased. The acetic anhydride is then distilled in a vacuum, the residue is poured into water, the water is boiled and the acetyl compound of anthraquinones 2:3-oxythionaphthene which has se arated in yellow flocks is filtered. This acety derivative is then saponified by heating it with alkali in water or alcohol, whereby the yellow acetyl compound becomes anthraquinone-2: 3-oxythionaphthene. The latter is 'a deep blue owder which passes towards orange on a dition of an acid. It is soluble to a brownish-yellow solution in hot nitrobenzene and to a blue-red solution in sulphuric acid, from which latter solution it is precipitated flocks by addition of water. With hydrosulphite and caustic soda solution it yields an olive vat having a 'lu-' minous blue fluorescence, but the reduced dyestufi has only slight afiinity for vegetable fibres.

Emample 2.

v 1 part of anthracene-2-thioglycol-3-carboxylic, acid is cautiously heated with 0.2

part of anhydrous sodium acetate in 5 parts" of acetic anhydride until evolution of car bon dioxide has ceased. The acetic anhydride is then distilled in a vacuum,'.the resiis a deep 'een-black powder which dissolves .in su phuric acid to a green solution and forms with hydrosulphite and caustic soda solution an olive-brown v-at which dyes cotton blue tints.

When 2-chloro-anthraquinone-3-carboxylic acid is heated together with thioglycolic acid at a higher temperaturea similar dyestufi is obtained.

E mample 5.

28 parts of anthraquinone-2:3-oxythio naphthene are suspended in 1000 parts of water, 100 parts of caustic soda solution are added and the mixture heated, at 100 while gradually adding about parts of may further be converted 2: 3-oxythionaphthene.

due is poured into water and the mixture is boiled and filtered to collect the clear yellow flocks of the acetyl-compound of anthrace'nc- This acetyl derivative is saponified by heating it with alkali in aqueous or alcoholic suspension or solution. The anthracene-2:3-oxythionaphthene thus formed is a clear brown powder which dissolves in sulphuric acid at first to a'red and then to a brown solution. On addition of water it is rue-precipitated in the form of brown flocks.

Emample 3.

acid are suspended in 100 parts of v thene which has been formed in an excellent yield by internal condensation and ring closure.

Emample 4;

parts of anthraquinone-2-thioglycol-3-.

carboxylic acid are heated with 500 parts of water in a closed vessel for several hours at 190-200 G, The anthraquinone-2z3-bisthionaphthene indigo is thus producedby ring closure and oxidation at the cost of a part of the parent material, the solid matter, after cooling, being filtered, boiled out with soda solution, again filtered, abundantly washed and dried.

The anthraquinone-Q:3-bis-thionaphtheneindigo corresponding with the following formula:

ammonium persulphate until the halo of a dab-test is no more violet but almost colorless: The anthraquinone-2:3-bis-thionaphthene indigo which has been formed is filtered, washed and dried.

Example 6'.

Aiter in sulphuric acid to an olive solution, yieldmg with hydrosulphite and caustic soda solution a brown vat from which cotton is dyed green tints.

Example 7'.-

' the following formula;

O 8 HN I=C \C t t is thus produced which separates in the olive vat.

form of a blue crystalline powder. After cooling the mixture is filtered and the dyestufl' washed with glacial acetic acid and water. i

It dissolves in sulphuric acid to a green solution from which water precipitates it in the form of blue flocks. It forms with (hydrosulphitc and caustic soda solution an olive brown vat which dyes cotton full, fast blue tints.

By substituting for the a-isatin-anilidc the equivalent quantit naphthalide. obtained from ,8naphthylamine by San meyers process) there is obtained a dyestufi' corresponding with the general formula:

which dyes cotton violetish-gre in avbrown- Instead of the ant ra uinone-2- thioglycol-3-carboxylic acid us in this example, the .anthraquinone-2: 3-oxythio naphthene can be condensed with isatin- 'anilide or another a-substituted isatin de- 1 rivative.

Emample 8.

the product is filtered, washed with alco 01 and water, and

it carboxylic acid are mixed with 25 p isatinwater in the lide in 300 several hours in a reflux dried. The new dyestuif corresponding with the general formula:

Emample 9. 32 parts of anthracene-2-thioglycol-3- parts of a-isatinanilide, 150 parts of acetic anhydride and 10 parts of anhydrous sodium acctate and the mixture is boiled for some hours in a reflux apparatus. After coolingthe condensation product which has been formed is filtered, washed with glacial acetic acid and water, and dried.

The new dyestulf corresponding with the following formula:

0/ \c t ll is a black green powder soluble in sulphuric acid to a brown solution from which. water precipitates it in the formof green flocks. With hydrosulphite and caustic soda solution it yields a, violet brown vat which dyes cotton pure green tints of surprising fastness.

If 20 parts of isatin be substituted for the no 25 parts of a-isatinanilide, a dyestufi' is produced which is a'blue-grey powder soluble in sulphuric acid to a red brown solution, from which it is precipitated by adding form of grey green flocks. 115 With hydrosulphite and caustic soda solu-' tion it yields a brown vat which .dyes cot ton valuable very fast grey tints.

7 Example 10.

26 parts of anthraoene-2z-3-oxythionaphthene are heated with 25 parts of a-isatinaniparts of pyridine. The formation of'dy'estufi is soon ended. The green dyestuif formed which is identical with that M of the ceding example is filtered, washed re with aitohol and vdrie Ewample I1. 82 parts of the dyestufi made in accordance with Example 7 from anthraquinone-2- zene and the mixture is gradually heated to the boiling point with 66 parts of-hromjne and then boiled for an hour in a reflux ap- Emample 13.

s filtered, washed paratus.

' After cooling, the mixture is filtered, washed with alcohol and dried. The new dyestufi is a blue violet crystalline powder, which dissolves in sulphuric acid to a green solution and yields-with hydrosulphite and caustic soda sOlutiOn a brown olive Vat which dyes cotton blue tints somewhat greener than those produced by the non-brominated dyestufi. v I

Example 12.

82 parts of the dyestuii from anthraquin0ne-2- hioglycol-3-carboxylic acid and g at 0 C. in 800 parts of chlorosulphonic acid, and the solution is mixed at 0 C. with 66'parts of bromine, whereupon it is stirred for an hour at ordinary temperature and then poured into The brominated dyestufl' corresponding probably with the general formula cz-isatinanilide are dissolved which has properties similar to those of the 2-thioglycol-3-carboxylic acid and az-isatinanilide are mixed in 1500 parts of nitrobenzene with 66 parts of bromine; the mixture is heated in the course of an hour to the boiling point and .then boiled gently for an hour in a reflux apparatus, After cooling, the bromination product is filtered, washed with alcohol and dried. It is a. grey green. powder which dissolves -in sulphuric acid to an olive solution, from which water precipitates it in the form of grey green flocks. With h drosulphite and caustic soda solution it orms a green vat which dyes cotton yellowgreen.

The dyestufl from anthracene-Q-thioglycol- 3-carboxylic acid and isatin brominated' in the samemanner yields a product which is agrey green powder, soluble in sulphuric acid to an olive solution, and yieldin with hydrosulphite and caustic soda. SOllltlOIl an green tints.

. The following table shows some of the characteristic propertiesof a number of dyestufl'swhich can'be made in accordance with this invention:

orange brown vat which dyes cotton grey Colour of Colour of solution Dyeing on Parent materials of the dyestuffs powden I L Colour of vat. cotton.

I. Anthraquinone-Z-thioglycol-3-carboxylio acid or anthraqui- Brown-olive.. Blue. none-2:3-oxythionaphthene-l-a-isatin anlllde. II. Idem+u-isatin anilide and brominatiou Brown-olive. Blue. III. Idem+B-nephthisatin-fi-naphthalide Brown-olive--." Violetish grey. IV. Idem+isatin Yellow-brown... Bordeaux. V; Idem+isatin and bromination violet red-. Yellow-brown... Bordeaux. VI. Idem+dibromoisatin Yellow-brown... Blue-red. VII. Idem+aeenaphthenequinone Brown Bluish bordeaux. VIII. Anthrequinone-2-thioglycol-3-carboxylic a d or anthra- Brown Bordeaux.

quinone-2z3-oxythionephthene acenaphthenequlnone and bromination. IX. Idem+thloisatin. Blue-red Heliotrope. X. Idem+thionaphth1satin V olet-brown.. Heliotrope. XI. Idem+5:Wdibromoisatinchlonda Violet Blue. XII. Idem+$chloroisatinchloride Violet. 0live-brown Blue. XIII. Idem-F5z7-dimethyhsatiu chloride. Violet. 0live-brown Bl e, XIV. Idem+7-methylisatin ch1oride Violet. 0live-brown Blue. XV. Idem+4-chloroA-methpxyisatinchloride.. Violet Olive Greenish-blue. XVI. Idem+4-1netl1oxyisat1n chloride Vio et... 0llve...; Greenish-blue. XVII. Anthrecene-2-th1oglycol 3-carboxylie aculor anthracenc- Green-black.-." Violet-brown. Pure green.

2:3-oxythionaphthene+asatm amhde. I XVIII. Idem-l-a-isatin anillde and brominatlon Grey-green-- Yellow-green. XIX. Idem+8-naphthlsat1n-B-napl1tl1alide Black-green. Green. XX. Anthracene-Z-th1oglycol-3Pcarboxy1ic acid or anthmeene- Blue-grey Blue-grey.

2:B-oxythionaphthene-i-xsatm. XXI. Idem+isatin and brominatlon rey-green" Orange-brown... Green-grey. XXII. Idem+dibromoisat1n BI'OWIL'. Greenish-grey. XXIII. Idom+thioisat1 Orange-brown." Dull blue-green.

rown Green. Dark green Olive-green Brown ..Green. Brown-bleck Orange-red Blue ey Greenlsh-groy. Green Blue-red. Yellow-brown Green. XXVI'II. Idem-i-G-bromo-lg2 naphthoq Green Blue-red Yellow-br0wn Green XXIX. Idem+5:T-dihromolsatin chloride Green-black..." Olive-grey... XXX Idem+7-methylisatin-Moluidido. Green-black--." Brown XXXI. Idem-i-fl-nephthisetinchloride Green-black-.- Brown- 'XXXII. Idem+u-naphthisatin-a-naphthellde Green-black Brown..-

The formula of the dyestuif XXV What we claim iscv 1. As new products of manufacture the herein described new indigoid dyestuffs of the general formula: a

wherein a: represents a hydrogen atom or an oxygen atom, and r,

n andm atoms of which two are carbon atoms adjacent to each other which at the same time appertain to an aromatic ring system, and of which vthe third is NH', -S- or C, which products form red to green and green-black powders soluble in concentrated sulphuric acid to oran red to green and brown solutions, yielding with hydrosulphite and caustic soda solution orange-brown to green vats which dye cotton fast blue-red to green and grey tints. y

'2. As new productsv of manufacture the herein described new i'ndigoid dyestuffs of the general formula:

wherein :2: represents a'hydrogen atom or an oxygen atom, and r, n and m atoms of which two are carbon atoms adjacent to each other which at the same time up ertain to an aromatic ring system, and 0 which the third is NH or S, which roducts form red green and green-blac powders soluble 1n concentrated sulphuric acid to orange-red to reen and brown solutions, yielding with by rosulphite and caustic soda solution orange-brown to green vatswhich dye cotton fast blue-red to green and grey tints;

3. As new products of manufacture the herein described new indigoid dyestuffs of the general formula:

wherein m represents a hydrogen atom or an oxygen atom, and r, 'n; and m atoms of which two are carbon atoms adjacent to each other which at the same time ap ertain to a rin of the benzene series, and 0 which the third is NH or S, which products form red .to green and green-black powders soluble in concentrated sulphuric acid to orange-red to green and brown solutions, yielding with hydrosulphite and caustic soda solution orange-brown to greenjvats which dye cotton fast-blue-red to greenand grey tints.

4. As new products of manufacture the herein described new indigoid dyestuffs of the general formula:

whereins represents a hydrogen atom or an oxygen atom, the atoms 0, and C, appertaimn to a ring of the benzene series, and ,1- is NI? or S, which roducts form red to green and een-blac powders soluble in concentrate sulphuric acid to orange-red to reenand brown solutions, yieldin with hyrosulphite and caustic soda so ution orange-brown togreen vats which dye cot-- ton ast blue-red to green and grey tints.

5. As new products of manufacture the herein described new indigoid dyestuffs of the general formula:

v a I V ism-c, l

. c c z I 5 whereinm represents a hydrogen atom or an oxygen atom, the atoms 0, and C, appertaining to a ring of the benzene series, which products form red to green and ecu-black powders soluble in, concentra sulphuric acid to orange red to green and brown solu-. tions, yielding withhydrosulphite and caustic soda, solution orange-brown to green 6. As new products of manufacture the. indigoid dyestufis of. the

wherein the atoms C and C appertain to a. ring of the benzene series, which products form brown-black to reen-black powders soluble in concentrated sulphuric acid to orange-red to olive solutions yielding with hydrosulphite -and caustic soda solution oran e-brown to green vats which dye cotton ast grey to green tints.

herein described general formula:

7. As a new product of manufacture the herein described new indigoid dyestufi hav- 25 ing probably the formula vats which dye cotton fast blue-red to green v and grey tints.

"BERTRAM MAYER. JAKOB WURGLER. 

